Synthetic resin metallic enamels



1950 LE venue K. osoAL EI'AL 2,493,020

SYNTHETIC RESIN "ETALLIC ENMELS Filed Feb. 10, 1948 I Y 0 $28 2 E88; w e m #m 0m 0 o: 52. mm ow mm on 3 ow mm 3 3 8 9 o. in: .P n n A 1 4 In 0 I, m W 8w N M a n Patented Jan. 3, 1950 SYNTHETIC RESIN METALLIC BNALIELS lie Verne Kenneth Osdal, Upper Darby, and Ralph Elike, deNemoni-eih ,WlliningtomDel.,a

corporation of Delaware Application February 10, 1048. Serial No. 7,480

5 Claims. (Cl. 200-22) This invention relates to new and novel coating compositions and, more particularly. to synthetic resin coating compositions having a polychromatic or metallic appearance.

Metallic coating compositions formulated with nitrocellulose lacquers have been in use for several years and have become very popular. particulsrly for use on automobiles, the metallic appearance being caused by the presence of a small amount of line aluminum iiakes uniformly dispersed in the lacquer.

7 However. attempts to produce similar metallic coating compositions with synthetic resin vehicles have been discouraging because, when a synthetic resin coating composition containing aluminum flakes was sprayed on a surface, the aluminum'flakes tended to migrate into colonies or fl l te parting an undesirable mottled appearance to the him. such migration does not occur in metallic nitrocellulose lacquers.

This invention therefore has as its principal object the production of synthetic resin coating compositions which will present a metallic appearance and a uniform surface exhibiting jno mottling.' flocking, or "flooding" when Sprayed.

Another ohiect is the production of such coatin: compositions which can be satisiactorily .patched" or repaired when necessary.

An additional object is the production of such coating compositions which will have a high build, a good gloss, and the desired metallic appearance.

A further object is the production of such coatlng compositions which will have flood outdoor durability.

A still further obiect is the production of such coating compositions which" will not "sag" on 9081118 and which may be reduced with an inexpensive hydrocarbon thinner.

These and other objects. which will become apparent as the description proceeds, are ac- -c'ompllshed in this invention by adding a p-dialkylaminoalkylmethacrylate polymer to a synthetic resin vehicle containing aluminum flakes.

The following examples are illustrative of the invention, the parts being by weight:

2 EXAMPLE 1 Metallic Blue bolting enamel Per cent Monoastral Blue as Bone black .31 Aluminum paste .10

Alkyd resin A solution (55% solution in high flash petroleum naphtha) 4.70

it) Alkyd resin B solution (50% solution in high flash petroleum naphtha) 10.08

Melamine formaldehyde solution (50% solution in hutyl alcohol 2.90

p Diethylaminoethylmethacrylate polymer solution (23% solution in acetone)- .00

Oil-modified phenol formaldehyde solution (60% solution in petroleum nloll ,15 Manganese naphthenate drier .10 Ethyl acetate 21.10 8 Low flash aliphatic petroleum naphtha--- 31; Toluol 13.55 Mineral spirits .06 High flash petroleum naphtha. 4.27

Alkyd res in A was a 52% linseed oil-modified slyceryl phthalate.

Alkyd resin 13 was a 45% linseed oil-modified I glyceryl phthalate.

The oil-modified phenol formaldehyde used in this and the following examples was a 32% China-wood oil-modified phenol formaldehyde resin.

The aluminum paste used in this and Examples 2-7, 13, and 14 had the following composition:

' Per cent Aluminum powder 08 V. M. l: P. naphtha 33 so Stearic acid l.

The manganese drier used in this and the following examples was a solution in mineral spirits containing 3% of the metal.

This enamel contained 0.12% of p-diethylaminoethylmethylacrylate based on the solids oi the alkyd resin present. the polymer having a high degree of tion, 1. e., a 50% solution in xylene had a viscosity of 80 polses.

Metallic Grow bakiao enamel Per cent Bone black .0! Lamp black .00 Red iron oxide--- .40 Rutile titanium dioxide 1.83

Alkyd resin A solution (55% solution in high flash petroleum naphtha) 10.81

Alkyd resin A solution (75% solution in high flash petroleum naphtha) Alkyd resin solution (50% solution in high flash petroleum naphtha) 54.70

Alkyd resin C was a 17% dehydrated caster oil/33% soya bean oil-modified pentaerythrltol glyceryl phthalate.

This enamel contained 0.83% oi p-diethylaminoethylmetl'iylacrylate based on the solids of the alkyd resin present, the polymer having a medium low degree of polymerization, i. e., 50% solution in xylene had a viscosity of 2 polses.

EXAMPLE 3 Metallic Gray baking enamel Per cent Bone black .00 Lamp black .07 Red iron oxide .40 Rutile titanium dioxide 1.82

Alkyd resin A solution (55% solution in high flash petroleum naphtha)..-- 10.15 Alkyd resin D solution (50% solution in high flash petroleum naphtha) 54.51 Alnd resin A solution (75% solution in high flash petroleum naphtha) .33 p Diethylaminoethylmethacrylate poly mer solution (50% solution in toluol) .07 Aluminum paste .00 Oil-modified phenol i'ormaldehyde solution (60% solution in petroleum xylol)- 1.32 iButanoi-modifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 07% hkh flash petroleum naphtha) 2.10 Manganese naphthenate drier .40 High flash petroleum naphtha. 25.39 Boya lecithin solution (50% solution in mineral spirits) .04 Creosole solution (1% solution in mineral spirits) .00

Alkyd resin D was a linseed oil/Chinawood oil-modified glyceryl phthalate.

This enamel contained 1% of p-diethylaminoethylmethacrylate based on the solids or the alkyd resin present, the polymer having a medium low degree of polymerization, i. e., a 50% solution in xylene had a viscosity of 2 poises.

EXAMPLE 4 Metallic Gray baking enamel Per cent lamp black. 1.67 Aluminum paste 1.13

Alkyd resin A solution solution in high flash petroleum naphtha) Alkyd resin E solution (50.5% solution in high flash petroleum naphtha) 48.20

Oil-modified phenol formaldehyde solution solution in petroleum xylol) .43 Butanol-modifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 67% high flash petroleum naphtha) 3.05 High flash petroleum naphtha 25.83 6 Diethylaminoethylmethacrylate poly mer solution (50% solution in xylene)- .70 Manganese naphthenate drier .54

Alkyd resin E was a 50% linseed oil-modified glyceryl phthalate.

This enamel contained 1% c1 fl-diethylaminoethylmethacrylate based on the solids of the alkyd resin present, the polymer having a medium low degree of polymerization, i. e., a 50% solution in xylene had a viscosity of 1.7 poises.

EXAMPLE 5 Metallic Gray baking enamel Per cent s Diethylaminoethylmethacrylate/ethylmethacrylate copolymer solution (50% Alkyd resin F was a 50% China-wood oil/soya bean oil-modified pentaerythritol phthalate.

The copolymer of B-diethylaminoethylmethacrylate had fi-dlethylaminoethylmethacrylate and 20% ethylmethacrylate.

This enamel contained 1% 01' the copolymer based on the solids of the alkyd resin present, the copolymer having a medium low degree of polymerization. i. e., a 50% solution in xylene had a viscosity of 1.3 poises.

Metallic Grail bakina enamel Per cent Bone black .07 Lamp black --A .58 ltediron oxide .43 Rutile titanium dioxide 1.83

Alkyd resin A solution (55% solution in high flash petroleum naphtha) 10.02

Alkyd resin A solution (75% solution in high flash petroleum naphtha) .33

Alkyd resin F solution (50% solution in high flash petroleum naphtha) 54.75 Aluminum paste .70

Oil-modified phenol formaldehyde solution (00% solution in petroleum xylol) 1.33 Butanol-modifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 87% high flash petroleum naphtha)- 2.27 Manganese naphthenate drier .40 Boys lecithin solution (50% solution in mineral spirits) .04 Creosole solution (1% solution in mineral spirits) .03 High flash petroleum naphtha 24.23 p-Diethylaminoethylmethacrylate polymer solution (50% solution in toluol) 1.33

This enamel contained 2.1% of p-diethylamlnoethylmethacrylate based on the solids oi the alkyd resin present, the polymer having a medium low degree of polymerization. l. e., a 50% solution in xylene had a viscosity of 2 poises.

EXAMPLE! Metallic Green baking enamel Per cent Monastral Green 3.39 Alkyd resin A solution (55% solution in high flash petroleum naphtha) 17.75 Alkyd resin E solution (50% solution in This enamel contained 0.44% of s-diethylaminoethylmethacrylate based on the solids of the alkyd resin present. the polymer having a low degree of polymerization, i. e., a 50% solution in xylene had a viscosity of 0.8 poise.

EXAMPLEB Metallic Green baking enamel Per cent Monostral Green Alkyd resin A solution (55% solution in high flash petroleum naphtha) 12.10 Alkyd resin E solution (50% solution in high flash petroleum naphtha) 45.50 Aluminum paste Butanol-modifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 07% high flash petroleum naphtha)- 2.50

Per cent Methanol 1.40 High flash petroleum naphtha. 32.50 Biol 3.33

s-Diethylaminoethyhnethacrylste polymer solution solution in toluol) .50

100.00 This enamel contained 1% of p-diethylaminoethylmethacrylate based on the solids oi the alkyd resin present, the polymer having a medium degree oi polymerization, i. e.. a 50% solution in xylene had a viscosity of 3.8 poises.

The aluminum paste of this example was similar to that of the previous examples, except it contained aluminum powder.

3 Metallic Green baking enamel Per cent Monastral Green 2.12 Aluminum paste .30 Alkyd resin A solution (55% solution in high flash petroleum naphtha) Alkyd resin G solution (50% solution in high flash petroleum naphtha) Butanol-modifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 67% high flash petroleum naphtha)- s-Diethylaminoethylmethacrylate polymer solution (50% solution in toluol) Methanol High flash petroleum naphtha Zylol EXAMPIE 10 Metallic Green baking enamel Monastral Green Alkyd resin A solution (55% solution in high flash petroleum naphtha) 10.02 Alkyd resin H solution (50% solution in high flash petroleum naphtha) Aluminum paste ,6 Diethylaminoethylmethacrylate poly- Per cent mer solution (50% solution in toluol) .51 Methanol 1.23 xylol 3.05 High flash petroleum naphtha 40.70 Butanol-rnodifled urea formaldehyde solution (33% solution in 33% butyl alcohol and 57% high flash petroleum naphtha) 2.20

Albd resin H was a 50% dehydrated caster oil-modified glyceryl phthalate.

This enamel contained 1% 01' p-diethylaminoethylmethacrylate based on the solids of the alkyd resin present, the polymer having a medium degree of polymerization. i. e., a 50% solution in xylene had a viscosity oi 8.3 poises.

Tnealuminum pastewasthesameasthatused in Example 3.

EXAMPLE 1i Metallic Maroon bokina enamel Per cent p Diethylaminoethylmethacryl ate polymer solution (50% solution in toluol) 2.63 Arylide Maroon (dark) 7.3 Aluminum paste .60 Alkyd resin A solution (55% solution in high flash petroleum naphtha) 6.49 Alkyd resin F solution (50% solution in high flash petroleum naphtha) 48.70 Butanol-modifled urea iormaldehyde solution solution in butyl alcohol) 0.22 Oil-modified phenol formaldehyde solution (00% solution in petroleum xylol) 1.12 cobalt naphthenate drier .15 Coconut oil fatty acids .10 V. M. I: P. naphtha 3.49 Hiah flash petroleum naphtha 21.07 100.00

in Example 8.

EXAMPLE 12 Metallic Gold baking enamel p Diethylaminoethylmethacrylate olymer solution (50% solution in toluol) 1.37 Hydrated iron oxide 7.12 Alkyd resin E solution (55% solution in high flash petroleum naphtha) 6.44 Alkyd resin F solution (50% solution in high flash petroleum naphtha) 42.67 Oil-modified phenol formaldehyde solution (60% solution in petroleum xylol) 1.87 Melamine formaldehyde solution (50% solution in butyl alcohol) 12.36 Aluminum paste .62 Mineral spirits 7.74 High flash petroleum naphtha 10.58 Cobalt naphthenate drier .73

100.00 This enamel contained 3.8% 0! p-dlethylaminoethylmethacrylate based on the solids of the alkyd resin present. the polymer having a medium low degree of polymerization, i. e., a 50% solution in nlene had a viscosity of 2 poises.

The aluminum paste was the same as that used in Example 0.

EXAMPLE 13 Metallic Aluminum air-drying enamel Per cent Aluminum paste 3.11

Albd resin E solution (50% solution in high flash petroleum naphtha) 37.33

p Diethylaminoethylmethacrylate (solids) 2.08

Oil-modified phenol iormaldehyde solution (00% solution in petroleum xylol) .58 Lead naphthenate drier .88 Manganese naphthenate drier .32 Cobalt naphthenate drier .27 Toluol 55.53

Per cent EXAMPLE 14 Metallic Blue air-drying enamel Per cent Aluminum paste 0.20 Iron Blue 2.52

Alkyd resin A solution (55% solution in high flash petroleum naphtha) 7.00

Alkyd resin E solution (50% solution in mineral spirits) 28.82

p-Diethylamlnoetlnrlmethacrylate polymer (solids) 2.05

Oil-modified phenol formaldehyde solution (60% solution in petroleum xylol) .34 Lead naphthenate drier .34 Manganese naphthenate drier .52 Cobalt naphthenate drier .23 High flash petroleum naphtha 2.39 Toluol 54.90

The fl-diethylaminoethylmethacrylate polymer was introduced in the same manner as described in Example 13.

This enamel contained 11% of il-diethylaminoethylmethacrylate based on the solids oi the alkyd resin present, the polymer having a low degree of polymerization.

As shown by Example 5, it is also possible to use copolymers of a p-dialkylaminoalkylmethacrylate in the practice of this invention.

The amount of fi-dialkylaminoalkylmethacrylate polymer necessary to impart the improved qualities to the metallic enamels of this invention depends upon the degree of polymerization of the polymer. These polymers can be obtained in various degrees of polymerization, and the degree oi polymerization is indicated by the viscosity of a 50% solution inxylene.

Referring to the chart herewith, two curves have been plotted, curve A representing the lower limits of polymer present which will produce the desired eflect, and curve B representing the upper limits thereof. As indicated by the circled dots on the chart, ii the degree of polymerization is high (viscosity of 40 poises or more), from 0.1% to 0.75% of the polymer will sumac: ii the degree of polymerization is medium high (viscosity of about 20 poises) from 0.15% to 3.5% will sufllce; if the degree of polymerization is medium (viscosity 01 about 10 poises), from 0.25% to 12% will sufllce; ii the degree 01 polymerization is medium low (viscosity of about 5 poises) at least 0.3% should be used; and ii the degree of polymerization is low (viscosity of about i poise or less), at least .4% should be used, all percentages being based on the weight of the clear vehicle solids.

Ii the quantity of a polymer having one of the higher degrees of polymerization is increased much above the percentages shown on this chart, the coating composition will gel.

It is preferred to use a polymer oi p-diethylaminoethylmethacrylate, and it is Iurther pieans-,oao

ferredtouse from 1% to 5% of one having aviscosity of .5 to noises in a 50% :n'lene solution.

In addition to those described in the above examples. other solvents for the polymers of p-dialkylaminoalkylmethacrylate may be used, such as benzene, the lower alcohols, methyl isobutyrate. mineral spirits, aldehydes, ketones, and naphtha.

It will be obvious from the wide range of alkyd resins disclosed in the above examples that any oil-modified alkyd resin may be used in the practice of this invention.

Any pigment or combination of pigments may be used as the coloring material in the production of the metallic enamels disclosed herein, the selection thereof for a particular color effect being readily apparent to those skilled in the art.

The coating compositions of this invention. when sprayed, produce a polychromatic or metallic iinish which is uniform and free from mottling. flooding. or sagging. They have good outdoor durability. high build, and high gloss, and they can be satisfactorily patched. Furthermore, they can he reduced with an inexpensive hydrocarbon thinner.

It is apparent that many widely different embodlments of this invention can be made without departing from the spirit and scope thereof and; therefore, it is not intended to be limited except as indicated inthe appended claims.

We claim:

1. A coating composition comprising an oilmodided alkyd resin .vehlcle. aluminum flakes. and a p-dialkylaminoalkylmethacrylate polymer. thelatterbeingpresentinanamountialiing within the range or the double curve represented btifi to.'i5$ whenithasahishdcarceofpolyi0 mensatlon..25% toii'lb whenithasamsdium degree or polymerization, and at least 4% when it has has a low degree of polymerisation. the percentages being based on the alkyd resin solids.

2. A coating composition comprising an oilmodified alkyd resin vehicle. aluminum flakes, and a. B-dialkylaminoalkylmethacrylate polymer. the latter being present in an amount Iallinl within the range of the double curve represented by .1% to .7596 when its viscosity is more than 40 pulses, .15% to 3.5% when its viscosity is 20 poises. .2% to 5% when its viscosity is 15 poim, 225% to 8.5% when its viscosity is 12.5 poises, 25% to 12% when its viscosity is 10 poises. at least 3% when its viscosity is 5 poises, and at least 4% when its viscosity is less than 1 poise, the percentages being based on the alkyd resin solids and the viscosities being measured on a solution in xylene.

3. A coating composition comprising an oilmodifled alkyd resin vehicle, aluminum flakes. and a p-dialkylamino alkyimethacrylate polymer having a viscosity of between .5 poise and 10 poises, the latter being present in an amount of from 1% to 5% based on the alnd resin solids and the viscosity being measured on a 50% solution in xylene.

4. The coating composition of claim 3 in which the polymer is p-diethylaminoethylmethacryiate.

5. The coating composition or claim 3 in which the oil-modified alkyd resin vehicle is a 50% linseed oil-modified glyceryl phthalate.

LE VERNE OSDAL. RALPH E. PIKE.

No references cited. 

1. A COATING COMPOSITION, COMPRISING AN OILMODIFIED ALKYD RESIN VEHICLE, ALUMINUM FLAKES, AND A B-DIALKYLAMINOALKYLMETHACRYLATE POLYMER, THE LATTER BEING PRESENT IN AN AMOUNT FALLING WITHIN THE RANGE OF THE DOUBLE CURVE REPRESENTED BY .1% TO .75% WHEN IT HAS A HIGH DEGREE OF POLYMERIZATION, .25% TO 5% WHEN IT HAS A MEDIUM DEGREE OF POLYMERIZATION, AND AT LEAST .4% WHEN IT HAS HAS A LOW DEGREE OF POLYMERIZATION, THE PERCENTAGES BEING BASED ON THE ALKYD RESIN SOLIDS. 